Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
  • A01N25/10—Macromolecular compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

• This invention relates to a biocide polymer material designed to inhibit the growth of micro-organisms in an aqueous solution, a device comprising said material, and a method to prepare said material. This invention also relates to a method to inhibit the growth of micro-organisms using said material.
• a photographic process includes several processing baths, which are aqueous solutions of photographically active substances.
• the photographic products are processed by successive immersion in these different solutions.
• fragments of gelatin from the photographic material being processed accumulate in the processing baths, favoring the growth of micro-organisms.
• biocides are conventionally added to processing baths. These biocides are generally used in excess of the quantity necessary to inhibit the growth of micro-organisms. These biocides can be costly and toxic. In particular, the disposal of such compounds in the drains causes problems in waste water treatment plants that use the action of micro-organisms to treat sewage.
• biocide used can be reduced by various means.
• patent application GB 2 223 662 describes an organic biocide chemically attached to a polymer by a bond that is cleaved by hydrolysis. The polymer is progressively hydrolysed, releasing the biocide in a controlled manner.
• this release of biocide does not depend on the presence of micro-organisms in the medium.
• Patent application EP 733303 describes a biocide material comprising an organic biocide immobilized on a polymer support that is insoluble in water. The biocide is attached to the polymer by hydrolytically stable bonds.
• Patent application EP 733304 describes a biocide material comprising a biocide of which the Log P value is at least 1.5, in which the biocide is immobilized on a support the surface of which is hydrophobic, by a mechanism of hydrophobic exclusion, P being the partition coefficent between n-octanol and water.
• biocide is used "as required" whenever microorganisms are present in the solution to be treated. It is desirable to have a biocide material comprising a biocide consumed "as required” solely in the presence of micro-organisms, having a high inhibiting efficiency.
• the invention relates to a biocide material comprising a water insoluble polymer support having immobilized thereon a biocide wherein the biocide material contains a water content from 30 to 60% based on the material weight.
• the invention also relates to a method of preparation of said material, which comprises the following steps: (i) Solubilizing a biocide in an organic solvent,
• the invention relates to a method to inhibit the growth of micro-organisms in an aqueous solution, by contacting the aqueous solution with the biocide material of the invention, and a device to implement this method.
• Biocides are compounds able to kill micro-organisms or inhibit the multiplication of micro-organisms such as bacteria, yeast, algae, molds, and lichens. Such compounds are known to the art. Examples of biocides are described in "Microbiocides for the protection of materials", by W. Paulus, published by Chapman Hall, 1993.
• biocides include sulfur- or nitrogen-containing heterocycles, compounds comprising active halogen groups, and quaternary ammonium salts.
• the biocides are isothiazolinones.
• the isothiazolinones useful in this invention can be represented by the formula: wherein R represents a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group, and R 1 and R each independently represent a hydrogen atom, a halogen, an alkyl group, or R and R jointly represent the atoms necessary to form a condensed carbocycle, preferably comprising 5 or 6 members, for example a benzene ring.
• Preferred biocides can be represented by the following formulae (I) or (II):
• wwhheerreeiinn RR 33 iiss aann aallkkyyll ggrroouupp ccoomm]prising 4 to 20 carbon atoms or an aryl group comprising 6 to 20 carbon atoms,
• R 5 and R 6 are selected from a hydrogen atom or a halogen atom, and R 4 is an alkyl group comprising 1 to 20 carbon atoms.
• Such biocides include for example Proxel® and Promexal® marketed by Zeneca, and Kathon® marketed by Rohm and Haas.
• the polymer support useful in the scope of the invention is any support, insoluble in water and on which a biocide can be immobilized.
• Useful polymers are for example the polymers obtained by condensation, such as polyesters, polyamides, polyurethanes, polyethers, epoxy resins, amino resins, phenol-aldehyde resins and acrylic polymers, and polymers derived from ethylenically unsatured monomers such as polyolefins, polystyrene, polyvinyl chloride, polyvinyl acetate, etc.
• the polymer support may have any of various shapes, for example sheets, beads, fibers, etc. It may be porous or non-porous.
• the support is usually inert towards the solutions to be treated. However, it can also be a resin that allows the composition of the solution to be treated to be modified in a controlled way. for example an ion exchange resin
• the biocide is dissolved in an organic solvent.
• an organic solvent for this purpose one or more biocides is dissolved in one organic solvent or in a mixture of organic solvents
• the organic solvent or solvents useful in the scope of the invention are for example heptane, hexane, dichloromethane, ethyl acetate, tetrahydrofuran or toluene.
• the solution concentration can vary largely.
• the concentration of biocide in the organic solvent or solvents is usually at least 0.2 mol/1, preferably between 0.2 mol/1 and 1 mol/1, and preferably between 0.25 mol/1 and 0.50 mol/1.
• the biocide material is formed by contact between the biocide solution and the water-saturated polymer support in conditions such that the biocide is immobilized on the polymer support.
• the biocide is immobilized by a mechanism of hydrophobic exclusion.
• the biocide must have a log P value of at least 1.5, P being the partition coefficient between n-octanol and water defined by
• Supports particularly suitable to immobilize the biocide by hydrophobic exclusion are supports with hydrophobic surfaces, for example cross- linked polystyrene beads, preferably porous. Such beads are marketed under the names Amberlite XAD-4® and Amberlite XAD-2®. In another embodiment, the support is a polyacrylic resin, for example Amberlite XAD-7®.
• the biocide material can be obtained merely by contacting the biocide solution with the water-saturated polymer support for a sufficient time to immobilize the biocide on the support.
• the contacting can be speeded up with stirring.
• the duration of contact between the polymer support and the biocide can range widely according to the support and the biocide selected. The optimum contact duration can be easily determined by those skilled in the art according to the substances present.
• the water and the solvent are eliminated by distillation.
• the water content of the biocide material is between 35 and 40% by weight of the material.
• a biocide material in the form of sheets, particles, fibers, etc. can be obtained.
• biocide material of the invention when it is contacted with an aqueous solution in which micro-organisms may grow, inhibits the growth of any such micro-organisms.
• the contact between the biocide material and the solution to be treated can be effected in any of various known ways.
• the biocide material of the invention or the device that makes use of such a material can be placed in a circuit in which the solutions to be treated flow, in order to optimize the contact between the micro-organisms and the biocide.
• the device can, for example, use the biocide material in the form of particles placed in a container through which the aqueous solution to be treated flows.
• the solution to be treated can also flow over strips of the biocide material.
• the biocide material is porous, the solution to be treated can be allowed to percolate through the biocide material.
• the material of the invention is especially well-suited to the treatment of photographic solutions for processing and washing photographic elements. The following examples illustrate the invention in detail.
• the flask maintained at 30°C, was inoculated so as to contain about 10 9 bacteria per ml. The number of growing colonies on inoculation and then after 1, 3, 5,
• Example 2 (Invention) The operating procedure of example 1 was repeated but the water in the biocide material was removed so as to obtain a water content of about 37%.

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• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• Environmental Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Toxicology (AREA)
• Hydrology & Water Resources (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

Applications Claiming Priority (3)

Publications (2)

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• 1998
  • 1998-11-25 FR FR9815009A patent/FR2786064B1/fr not_active Expired - Fee Related
• 1999
  • 1999-11-18 CA CA002351439A patent/CA2351439A1/en not_active Abandoned
  • 1999-11-18 DE DE69902105T patent/DE69902105T2/de not_active Expired - Fee Related
  • 1999-11-18 AU AU19665/00A patent/AU1966500A/en not_active Abandoned
  • 1999-11-18 WO PCT/EP1999/008863 patent/WO2000030443A1/en active IP Right Grant
  • 1999-11-18 EP EP99963310A patent/EP1133228B1/de not_active Expired - Lifetime
  • 1999-11-18 JP JP2000583341A patent/JP2002530298A/ja not_active Ceased
  • 1999-11-18 US US09/856,967 patent/US6437021B1/en not_active Expired - Fee Related
• 2001
  • 2001-05-23 NO NO20012525A patent/NO20012525D0/no not_active Application Discontinuation

Non-Patent Citations (1)

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